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WO2005114161A1 - Etalonnage d'electrode - Google Patents

Etalonnage d'electrode Download PDF

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Publication number
WO2005114161A1
WO2005114161A1 PCT/GB2005/002012 GB2005002012W WO2005114161A1 WO 2005114161 A1 WO2005114161 A1 WO 2005114161A1 GB 2005002012 W GB2005002012 W GB 2005002012W WO 2005114161 A1 WO2005114161 A1 WO 2005114161A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
boranocarbonate
solution
corm
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/GB2005/002012
Other languages
English (en)
Inventor
Roberto Angelo Motterlini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hemocorm Ltd
Original Assignee
Hemocorm Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hemocorm Ltd filed Critical Hemocorm Ltd
Priority to EP05744137A priority Critical patent/EP1763670A1/fr
Priority to US11/596,977 priority patent/US20080121012A1/en
Publication of WO2005114161A1 publication Critical patent/WO2005114161A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/4163—Systems checking the operation of, or calibrating, the measuring apparatus
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/004—CO or CO2

Definitions

  • This invention relates to a method of calibrating a CO-concentration sensing electrode, and to such an electrode calibrated by the method.
  • transition metal carbonyls have the inherent ability to liberate CO under appropriate conditions and function as CO-releasing molecules (CO-RMs) in biological systems (refs. 2-4).
  • the first two carbonyl complexes initially identified and possessing such prerequisites were manganese decacarbonyl ( [Mn 2 (CO) 10 ] ) and tricarbonyldichlororuthenium(II) dimer ( [Ru (CO) 3 C1 2 ] 2 ) , which have been subsequently termed CORM-1 and CORM-2, respectively (ref. 4).
  • Tricarbonylchloro (glycinato) ruthenium (II) (CORM-3), which can be obtained by coordinating the aminoacid glycine onto the metal center, is fully soluble in water and rapidly liberates CO in vitro, ex-vivo and in vivo biological models (ref. 4) . It has been shown that CORM- 3 protects myocardial tissues against ischemia- reperfusion injury both ex-vivo (ref. 5) and in vivo (ref. 6) and prolongs the survival of cardiac allografts in mice (ref. 5) . More recently, evidence has been provided showing important vasodilatory properties of
  • CORM-3 through mechanisms that involve guanylate cyclase and potassium channel activation (ref. 7).
  • Recently sodium boranocarbonate Na 2 [H 3 BC0 2 ] , here termed CORM-A1
  • CORM-A1 sodium boranocarbonate
  • WO 2005/013691 and ref. 9 sodium boranocarbonate
  • a method of calibrating a CO-concentration sensing electrode wherein at least one solution containing a known concentration of CO obtained by dissolving a predetermined amount of a CO-releasing boranocarbonate compound is employed as a standard solution contacted with the electrode to obtain an output from the electrode enabling its calibration.
  • a plurality of standard solutions of different CO-concentration are contacted with the electrode to obtain a plurality of outputs enabling its calibration.
  • Boranocarbonates are a group of compounds which can loosely be described as carboxylate adducts of borane and derivatives of borane.
  • Boranocarbonates generally contain a group of the form -COO " or COOR (where R is H or another group) attached to the boron atom, so that they may be called boranocarboxylates or carboxyboranes, but the term boranocarbonate seems to be preferred.
  • the compound K 2 (H 3 BCOO) and the related K(H 3 BCOOH) are described in reference 8, where K 2 (H 3 BCOO) is used for producing Tc carbonyls.
  • K 2 (H 3 BCOO) is used for producing Tc carbonyls.
  • a boranocarbonate has the molecular structure including the moiety
  • the structure generally is an anion. It may be a divalent anion when one (COQ) is present as (COO " ) . If the structure is an anion, a cation is required. Any physiologically suitable cation may be employed, particularly a metal cation such as an alkali metal ion e.g. K + or Na + or an alkaline earth metal cation such as Ca ++ or Mg ++ . Alternatively non-metal cations might be employed, such as NR 4 + where each R is H or alkyl (preferably of 1 to 4 carbon atoms) or PR 4 + where R is alkyl (preferably of 1 to 4 carbon atoms) .
  • NR 4 + where each R is H or alkyl (preferably of 1 to 4 carbon atoms)
  • PR 4 + where R is alkyl (preferably of 1 to 4 carbon atoms) .
  • the cation may be selected in order to achieve a desired solubility of the compound.
  • y is 1.
  • x is 3 and y is 1, since the presence of three H atoms attached to B seems to promote CO release.
  • Q is 0 " , OH or OR.
  • the boranocarbonate is soluble and may be present in the solution contacting the electrode in a suitable solvent, which typically contains or is a protic solvent, since protons promote the CO release.
  • the solvent is aqueous (containing at least some water) . Water may be used, or the aqueous solvent may be in suitable cases a biological fluid or buffer, such as plasma or blood.
  • the solutions can be provided for contact with the electrode containing dissolved CO, already released by the boranocarbonate. Release of CO, before or during contact with the electrode, may be triggered by change of condition (e.g. pH or temperature) .
  • Preferred boranocarbonates are K 2 (H 3 BCOO) , Na 2 (H 3 BCOO), K(H 3 BCOOH) and Na (H 3 BCOOH) .
  • the invention is therefore based on use of a solution containing, in a reproducible manner, a predetermined amount of dissolved CO, derived from a boranocarbonate (or mixture of boranocarbonates).
  • the solution generally has a predetermined pH and temperature, to ensure the desired CO concentration, particularly if the release of CO is pH-dependent and/or temperature dependent.
  • the invention provides a CO- concentration detecting electrode calibrated by the method described above.
  • the electrode is in combination with a data set relating its output to CO- concentration of a liquid medium contacting it .
  • the data set is derived from the calibration procedure and may be a data table or graph, and may be stored in visible form, e.g. on paper, or in electronic or other computer- readable form, e.g. as a data set in a computer-readable memory .
  • the invention provides a kit for use in calibration of a CO-concentration electrode comprising: (a) at least one sample of a CO-releasing boranocarbonate compound in a predetermined amount in a sealed first container, (b) at least one aqueous solution in a predetermined amount in a second container.
  • the kit may also include a CO-concentration electrode.
  • the kit may have a plurality of said samples (a) and a plurality of said solutions (b) .
  • the or each solution (b) may be a buffer solution of predetermined pH. Preferably there are a plurality of said solutions
  • kits having respectively different pH values; an example is three solutions of pH 3, 6 and 7.4 respectively.
  • the kit has means for maintaining at least said sample (a) at a predetermined temperature.
  • a suitable temperature is in the range 0-10°C, e.g. 4°C.
  • the boranocarbonate is stored in an inert gas atmosphere, e.g. argon or nitrogen.
  • the invention is applicable to CO-concentration electrodes for detecting CO in solution, such as an electrochemical electrode.
  • An example of a suitable electrochemical sensor for detecting CO in solution is described in US Patent 4,729,824. Another known form of CO electrode is described below.
  • Figure 1 shows carbonmonoxy myoglobin (MbCO) and deoxy-myoglobin absorption spectra.
  • Figure 2 shows a carbonmonoxy myoglobin (MbCO) and deoxy-myoglobin absorption spectra, a graph showing the concentration of MbCO over time, and a graph with a correlation curve.
  • Figure 3 shows current-time curves using an amperometric electrode sensitive to CO with the compounds CORM-Al and iCORM-Al, and a graph with a correlation curve .
  • the release of CO from CORM-Al was assessed spectrophotometrically by measuring the conversion of deoxymyoglobin (deoxy-Mb) to carbonmonoxy myoglobin (MbCO) in a manner previously reported (refs. 3, 4, 5) .
  • a small aliquot of CORM-Al 60 ⁇ M final concentration was added to 1 ml deoxy-Mb (*53 ⁇ M) in phosphate buffer and changes in the Mb spectra were recorded over time.
  • This CO electrode is a membrane-covered amperometric sensor which has been designed on a basic operating principle similar to the nitric oxide (NO) sensor (ISO-NOP series, World Precision Instruments) .
  • the CO sensor can be connected to the ISO- NO Mark II meter for detection of the current signals providing that the poise potential is set to a different value (900 V for CO as opposed to 860 mV for NO) .
  • CO diffuses through the gas permeable membrane and is then oxidized to C0 2 on the working electrode. This oxidation creates a current whose magnitude can be related directly to the concentration of CO in solution.
  • the CO sensor was used to generate standard curves and calculate the rates of CO release from CORM-Al at different pHs and temperatures.
  • the electrode was immersed into the solutions at different pHs and equilibrated for 30 min prior to addition of CORM-Al.
  • the solutions were maintained at the desired temperature using a Grant W6 thermostat (Cambridge, England) .
  • CORM-Al liberates CO in a pH- and temperature-dependent manner
  • the spectrophotometric assay that detects the formation of carbonmonoxy myoglobin (MbCO) from deoxy-Mb has been shown to be a reliable method for assessing the extent and kinetics of CO liberation from CO-RMs (refs. 3, 4, 5) .
  • the conversion of deoxy-Mb to MbCO can be followed over time by measuring the changes in the absorption spectra of this protein.
  • PBS solution Phosphate buffered saline (PBS) solutions are prepared by adding one tablet of this compound (purchased from Sigma Chemicals, catalogue number P-4417) to 150 ml of distilled water. The pH of each solution is then adjusted to the desired pH (7.4, 6 or 4 ) and the volume brought to 200 ml.
  • the solution prepared in this way will have the following composition: 0.01 M phosphate, 0.0027 M potassium chloride and 0.137 M sodium chloride .
  • the CO sensor is connected to an ISO Mark II nitric oxide (NO) meter from World Precision Instruments and the general procedures of operation are exactly the same as reported in their manual of instructions. The only difference is the poise potential that is set to 930 mV for the detection of CO in solution.
  • a data acquisition system (Chart 4.2 from PowerLab ADInstruments) is used for collection of the data.
  • the electrode is connected to the NO meter (switched on) for a few hours before use. During this time the background current (observed as the baseline) will fall as the electrode polarizes. Eventually the baseline remains relatively stable and the instrument can be zeroed ready for use.
  • the CO sensor is an electrochemical instrument and is sensitive to temperature so that all the measurements are done at precise temperatures.
  • the calibration of the CO electrode using CORM-Al is conducted by continuously mixing the solution with a magnetic stirrer.
  • the calibration kit consists of the following items:
  • the calibration is carried out at the temperature at which subsequent measurements of CO are to be made. This can be accomplished by placing the vial and stand in a water bath at the appropriate temperature, and allowing the temperature of the solution in the vial to equilibrate with the water bath.
  • a calibration curve can then be created by plotting the changes in current (pA) against the changes in concentration ( ⁇ M) . (Since the reaction of CORM-Al goes to completion (see ref. 8), the amount of CO generated in the solution will be equal the amount of CORM-Al added. The final concentration of CO will be equal to the diluted concentration of CORM-Al in the solution) . The slope of this curve will indicate the sensitivity of the probe. Once the sensitivity of the probe has been ascertained, the sensor is ready to use experimentally.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analysing Biological Materials (AREA)

Abstract

L'invention concerne un procédé et un nécessaire pour l'étalonnage d'une électrode de détection de concentration de monoxyde de carbone (CO). Ledit procédé fait appel à une solution étalon obtenue par dissolution d'une quantité prédéterminée d'un boranocarbonate libérant du CO afin d'obtenir une concentration connue de CO.
PCT/GB2005/002012 2004-05-20 2005-05-20 Etalonnage d'electrode Ceased WO2005114161A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP05744137A EP1763670A1 (fr) 2004-05-20 2005-05-20 Etalonnage d'electrode
US11/596,977 US20080121012A1 (en) 2004-05-20 2005-05-20 Electrode Calibration

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0411261.1 2004-05-20
GBGB0411261.1A GB0411261D0 (en) 2004-05-20 2004-05-20 Electrode calibration

Publications (1)

Publication Number Publication Date
WO2005114161A1 true WO2005114161A1 (fr) 2005-12-01

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Application Number Title Priority Date Filing Date
PCT/GB2005/002012 Ceased WO2005114161A1 (fr) 2004-05-20 2005-05-20 Etalonnage d'electrode

Country Status (4)

Country Link
US (1) US20080121012A1 (fr)
EP (1) EP1763670A1 (fr)
GB (1) GB0411261D0 (fr)
WO (1) WO2005114161A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8697747B2 (en) 2009-03-05 2014-04-15 The Uab Research Foundation Enhancing coagulation or reducing fibrinolysis

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3997296A (en) * 1975-02-06 1976-12-14 Spex Industries Inc. Primary standards
DE3514346A1 (de) * 1985-04-20 1986-10-23 Rolf Prof. Dr.med. 6500 Mainz Zander Eine calibrierfluessigkeit mit konstantem co(pfeil abwaerts)2(pfeil abwaerts)-gehalt
EP0530871A1 (fr) * 1991-08-02 1993-03-10 INSTRUMENTATION LABORATORY S.p.A. Méthode de production d'une substance de calibration en phase liquide, avec une concentration en CO2 prédeterminée, appropriée à la calibration des instruments analytiques, tels que des analyseur des gaz dans le sang
US5659125A (en) * 1995-06-07 1997-08-19 Nighthawk Systems, Inc. Automatic calibration method for carbon monoxide monitors
WO2001025243A1 (fr) * 1999-10-05 2001-04-12 Mallinckrodt Inc. Source de monoxyde de carbone utile dans la preparation de complexes carbonyle/metaux de transition
US6632674B1 (en) * 1999-03-31 2003-10-14 Industrial Scientific Corporation Method of testing gas detection instruments and associated apparatus
GB2395432A (en) * 2002-11-20 2004-05-26 Northwick Park Inst For Medica Therapeutic delivery of carbon monoxide using metal carbonyl complexes

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4729824A (en) * 1982-05-11 1988-03-08 Giner, Inc. Gas sensor and method of using same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3997296A (en) * 1975-02-06 1976-12-14 Spex Industries Inc. Primary standards
DE3514346A1 (de) * 1985-04-20 1986-10-23 Rolf Prof. Dr.med. 6500 Mainz Zander Eine calibrierfluessigkeit mit konstantem co(pfeil abwaerts)2(pfeil abwaerts)-gehalt
EP0530871A1 (fr) * 1991-08-02 1993-03-10 INSTRUMENTATION LABORATORY S.p.A. Méthode de production d'une substance de calibration en phase liquide, avec une concentration en CO2 prédeterminée, appropriée à la calibration des instruments analytiques, tels que des analyseur des gaz dans le sang
US5659125A (en) * 1995-06-07 1997-08-19 Nighthawk Systems, Inc. Automatic calibration method for carbon monoxide monitors
US6632674B1 (en) * 1999-03-31 2003-10-14 Industrial Scientific Corporation Method of testing gas detection instruments and associated apparatus
WO2001025243A1 (fr) * 1999-10-05 2001-04-12 Mallinckrodt Inc. Source de monoxyde de carbone utile dans la preparation de complexes carbonyle/metaux de transition
GB2395432A (en) * 2002-11-20 2004-05-26 Northwick Park Inst For Medica Therapeutic delivery of carbon monoxide using metal carbonyl complexes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALBERTO R ET AL: "SYNTHESIS AND PROPERTIES OF BORANOCARBONATE: A CONVENIENT IN SITU CO SOURCE FOR THE AQUEOUS PREPARATION OF Ä99MTC(OH2)3(CO)3Ü+", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, vol. 123, 13 March 2001 (2001-03-13), pages 3135 - 3136, XP001120003, ISSN: 0002-7863 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8697747B2 (en) 2009-03-05 2014-04-15 The Uab Research Foundation Enhancing coagulation or reducing fibrinolysis

Also Published As

Publication number Publication date
EP1763670A1 (fr) 2007-03-21
GB0411261D0 (en) 2004-06-23
US20080121012A1 (en) 2008-05-29

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